Catalyst system

ABSTRACT

A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of Group Va or Group VII oxygen mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.

BACKGROUND OF THE INVENTION

This invention relates to propylene polymerization catalysts andparticularly relates to catalyst systems which produce commerciallyacceptable levels of low molecular weight and, especially, substantiallyamorphous polymers as determined by the amount of polymerized productwhich is soluble in n-hexane at room temperature ("Hexane Solubles").

The polymerization of propylene to normally-solid, substantiallycrystalline polymers using heterogeneous catalysts comprising transitionmetal halides and aluminum alkyls now is well known in the art. However,there is a continuing need in the industry for complete catalyst systemswhich produce a high yield, as measured by the grams of crystallineproduct per gram of transition metal halide consumed, while producing aminimum amount of Hexane Solubles. In a slurry polymerization processwhich uses a hydrocarbon solvent, such as n-hexane, amorphous and lowmolecular weight polymer accumulates in the solvent which necessitatesextensive solvent purification procedures. Since the economic value ofsuch n-hexane-soluble polymer is lower than normally-solid,substantially crystalline product, the overall process becomes lessefficient as the amount of Hexane Solubles increases. A commerciallydesirable catalyst system would produce low amounts of Hexane Solubleswhile maintaining reasonable yields. The product produced using suchcatalyst system desirably has acceptable odor and environmentalqualities. Also desirable is a low concentration of residual titanium.

In a solventless, liquid-phase bulk polymerization or in a gas phaseprocess, the production of polymers which contain more than about 2% ofHexane Solubles requires a separate extraction procedure to producecommercially acceptable products and makes these inherently efficientprocesses uneconomical. Therefore, polymerization processes whichproduce low amounts of Hexane Solubles while not adversely affectingpolymerization yield are in demand.

Various catalyst modifiers in addition to transition metal halides andaluminum alkyls have been disclosed to minimize Hexane Solubles inalphaolefin polymerizations. Such modifiers include aromatic oraliphatic amines, esters, amides, phosphites, phosphines, phosphineoxides, aldehydes, tetraorganosilyl compounds such as tetraalkyl-,tetraaryl- and tetraalkoxysilanes, sterically hindered cyclic amines,amine N-oxides and organotin sulfides. Known catalyst modifiers includethe combination of hydrogen sulfide, sulfur dioxide or bis-(tributyl)tinsulfide with an aromatic amine or amine oxide such as lutidine,collidine (2,4,6-trimethylpyridine) and lutidine-N-oxide. Specificcatalyst systems including such combinations of modifiers are describedin U.S. Pat. Nos. 3,950,268 and 4,072,809 both incorporated by referenceherein. Although such modifiers do tend to decrease Hexane Solubles,they or their reaction products may produce undesirable odor or othereffects in polymeric product.

Molecular weights of alpha-olefin polymers have been controlled byaddition of "hydrogen active" compounds such as mineral acids to theolefin stream or directly to the polymerization reaction (U.S. Pat. No.3,161,628). U.S. Pat. No. 2,971,950 discloses adding anhydrous hydrogenhalide or alkyl halide to an alpha-olefin polymerization to controlmolecular weight. U.S. Pat. No. 3,271,381 uses 0.5 to 3 gram-equivalentsof a strong acid per gram-atom of titanium to control molecular weightof polyolefins.

The use of halogen acids, e.g., HCl or HBr, to treat catalyst supportsis taught in U.S. Pat. Nos. 3,658,722 and 3,888,789. Hydrogen chloridegas has been incorporated in alpha-olefin polymerization to produceelastomers (U.S. Pat. No. 3,563,964) and to change polymerization to acationic process (U.S. Pat. No. 3,692,712). U.S. Pat. No. 3,275,569teaches reducing titanium tetrahalide with aluminum in the presence of ahydrogen halide to form a polymerization catalyst component, while U.S.Pat. No. 2,256,264 teaches a polymerization catalyst system from ahalogenated metal of groups IVa, Va, or VIa (e.g. TiCl₄), aluminumchloride, hydrogen chloride and powdered aluminum. U.S. Pat. No.3,121,064 teaches regenerating a titanium halide catalyst component withdry halogen chloride. Sulfur dioxide and sulfur trioxide have beendisclosed to treat an olefin polymerization catalyst componentconsisting of a titanium or vanadium compound supported on a metal oxideor hydroxide (U.S. Pat. No. 4,027,088 and British Pat. No. 1,492,549).

Certain mineral and organic acids and anhydrides have been used inolefin polymerization systems which do not employ anorganoaluminum-transition metal compound catalyst to form crystallinepolymers. References to such systems are made in U.S. Pat. Nos.3,426,007, 3,476,731, 3,497,488, Re 29,504, 3,676,523, 3,686,351,3,850,897, 3,896,087, and 4,029,866.

Carboxylic acids have been added to ethylene polymerization to reducedeposition of polymer on reactor walls (U.S. Pat. No. 3,082,198). Alkalimetal salts of inorganic oxyacids have been used in an olefinpolymerization catalyst comprising an aluminum sesquihalide and atransition metal halide (U.S. Pat. No. 3,400,084). Acid and base ionexchange resins have been used in olefin polymerization systems toproduce crystalline polymer (U.S. Pat. No. 3,595,849).

An object of this invention is to produce catalyst modifiers whichdecrease Hexane Solubles while maintaining reasonable polymerizationactivity. A further object of this invention is to produce a polymericproduct having acceptable odor. Other objects are described herein.

SUMMARY OF THE DISCLOSURE

A propylene polymerization catalyst is formed by incorporating into acatalytic mixture comprising a transition metal compound and anorganoaluminum compound, effective amounts of Group Va or Group VIIoxygen mineral acids whereby the amount of n-hexane-soluble polymericproduct is decreased.

BRIEF DESCRIPTION OF THE INVENTION

Advantages of this invention include catalyst system which produces acommercially acceptable amount of Hexane Solubles polymer whilemaintaining reasonable catalytic activity. Further, catalyst modifiersof this invention generally do not introduce unacceptable levels ofodor-forming compounds nor known compounds which may be environmentallydetrimental. Since the modifiers of this invention are mineral acids,possibly harmful complex organic compounds are not added to thepolymerization system.

Modifiers of this invention are Group Va or Group VII oxygen mineralacids. These modifiers include oxygen mineral acids of nitrogen,phosphorous, and chlorine and specifically include nitric acid,phosphoric acid, phosphorous acid and perchloric acid. Examples of otherGroup VA and Group VII oxygen mineral acids include nitrous acid, peroxonitric acid, peroxonitrous acid, nitroxylic acid, hyponitrous acid,diphosphoric acid, triphosphoric acid, polyphosphoric acid, metaphosphoric acid, trimeta phosphoric acid, tetra meta phosphoric acid,peroxo (mono) phosphoric acid, peroxo diphosphoric acid, hydrophosphoricacid, diphosphoric (III, IV) acid, diphosphorous acid, hypophosphorousacid, arsenic acid, arsenious acid, hexahydroxoantimonic acid, chloricacid, chlorous acid, hypochlorous acid, bromic acid, bromous acid,hypobromous acid, periodic acid, hypobromous acid, periodic acid, iodicacid, permanganic acid, manganic acid, pertechnetic acid, perrhenic acidand rhenic acid. Preferably, these mineral acid modifiers are inconcentrated aqueous solutions, although less concentrated solutions areuseful. For example, preferred concentrations of specific acids arenitric acid--about 70 wt. %, HNO₃, phosphoric acid--about 85 wt. %, H₃PO₄, phosphorous acid--about 30 wt. %, H₃ PO₃, and perchloricacid--about 72 wt. % HClO₄.

The exact amount of the modifiers useful in this invention variesdepending upon the specific modifier, the precise make-up of the othercatalyst components, and the polymerization conditions. Typicallyeffective amounts range from a molar ratio to the transition metalcompound of about 0.01 to 1 to about 0.7 to 1 and preferably about 0.02to 1 to about 0.5 to 1 and most preferably about 0.04 to 1 to about 0.1to 1. The concentration of modifiers must be sufficient to show adecrease in Hexane Solubles. At reasonably low levels of modifiers, theyield of polymeric product is not seriously affected. However, at higherlevels of modifier the yield of product tends to decrease. An optimumlevel of modifier will produce both acceptable yields of Hexane Solublesand polymeric product.

For the purpose of determining Hexane Solubles, the "n-hexane" used is amixture of substantially C-6 hydrocarbons containing about 85-88 wt. %normal hexane.

Although not preferred, modifiers of this invention can be utilized inconjunction with effective catalyst coadditives such as alkyl silicates,orthosilicate esters, esters, Lewis bases such as phosphines,phosphites, phosphates, phosphine oxides, aromatic amines, amine oxides,tertiary aliphatic amines .[.an.]. .Iadd.and .Iaddend.ethers or anorganometallic chalcogenide such as bis(trialkyl)tin sulfide. Theseadditional additives can be present in minor amounts ranging from aboutone-tenth to 30 mol percent and preferably about 1 to 20 mol percent ofthe transition metal halide in the catalyst system. Two or more suitableoxygen mineral acids can be combined and used in this invention. Inaddition, the oxygen mineral acids useful in this invention can be mixedwith other compatible mineral acids for use in this invention.

The catalyst system described in this invention contains (a) anorganoaluminum compound and (b) a transition metal compound in additionto minor amounts of other additives.

Useful organoaluminum compounds include trialkylaluminum,dialkylaluminum halides, mixtures of trialkylaluminum withdialkylaluminum halides and mixtures of trialkylaluminum withalkylaluminum dihalides. Also catalytic effective amounts of mixtures oftrialkylaluminums and dialkylaluminum halides can be used in conjunctionwith alkylaluminum dihalides. Useful halides include bromides andchlorides and useful alkyl radicals contain from two to about six carbonatoms. The preferable halide is chloride and the preferable alkylradical is ethyl. Diethylaluminum chloride (DEAC) is most preferable. Ina trialkylaluminum-dialkylaluminum halide mixture, the preferred amountof trialkylaluminum is about 20 to 50 mol percent. In atrialkylaluminum-alkylaluminum dihalide mixture, the preferred amount oftrialkylaluminum is about 30 to 70 mol percent and most preferably about40 to 60 mol percent.

The transition metal compounds useful as a component in the catalystsystem of this invention are compounds of transition metals of GroupsIVB, VB and VIB of the Periodic Table. Preferably, the transition metalcompound is a halide of titanium, vanadium, chromium, or zirconium. Mostpreferably, titanium trichloride and especially activated titaniumtrichloride is used. Titanium trichloride can be activated to a highdegree of polymerization activity by chemical and physical means. Oneuseful activated titanium trichloride has an approximate stoichiometricformula of TiCl₃.1/3 AlCl₃ and has been comminuted. Further, titaniumtrichloride can be activated by forming adducts with Lewis bases such asethers or by supporting the titanium trichloride on a catalyticallyinert substance such as a metal oxide or salt. One suitable titaniumtrichloride is described in U.S. Pat. No. 3,984,350 incorporated byreference herein.

The molar ratio of transition metal halide to organoaluminum compound ina catalyst system can range from about one-tenth to about 10, typicallyis about 1 to 3 and preferably is about 2. The amount of catalyst in apolymerization depends on the reactor size and type and on the amountand type of olefin monomer and is known to the skilled artisan.

Preferably, a catalyst system package is made prior to introduction ofsuch package into a polymerization reactor. Catalyst components can bemixed together in any order, typically using an inert hydrocarbon or themonomer as a suitable medium, although preferably the modifiers firstare added to an inert hydrocarbon solution of the organoaluminumcompound. Preferably, the catalyst modifiers of this invention are addedslowly while mixing to a solution of organoaluminum compound in an inerthydrocarbon. Such resulting mixture is added to a suspension oftransition metal compound in an inert hydrocarbon. After complete mixingthe resulting catalyst package can be introduced into a polymerizationreactor.

Since the catalyst systems used in this invention are sensitive tooxygen and moisture, suitable precautions should be taken duringcatalyst preparation, transfer and use.

The polymerization process of this invention can be practiced atpressures ranging from about atmospheric to about 20,000 p.s.i.g. andpreferably from about 30 to 1000 p.s.i.g.

The polymerization time depends on the process used. In batch processesthe polymerization contact time usually is about one-half to severalhours and typically is one to four hours in autoclave processes. In acontinuous process, contact time in the polymerization zone iscontrolled as required and typically ranges from about one-half toseveral hours. Since in this type of process unreacted monomercontinuously can be recycled into the polymerization zone, the contacttime can be shorter than in a batch process.

The liquid organic solvents used in the slurry polymerization techniqueinclude aliphatic alkanes and cycloalkanes such as pentane, hexane,heptane or cyclohexane; a hydrogenated aromatic compound such astetrahydronaphthalene or decahydronaphthalene; a high molecular weightliquid paraffin or mixtures of paraffins which are liquid at thereaction temperature; an aromatic hydrocarbon such as benzene, tolueneor xylene; or a haloaromatic compound such as chlorobenzene,chloronaphthalene or o-dichlorobenzene. Other suitable solvents includeethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene,diethylbenzenes, mono and di-alkylnaphthalenes, n-pentane, n-octane,isooctane and methyl cyclohexane. Preferably, liquid hydrocarbons areused; most preferably, n-hexane is the polymerization medium. Althoughthe nature of the solvent can be varied considerably, the solvent shouldbe liquid under the reaction conditions and should be relatively inert.Advantageously, the solvent used can be purified prior to use bydistillation, by reaction with an aluminum alkyl, or by adsorption withmolecular sieves.

The polymerization temperature depends upon the specific catalyst systemused and can range from below about 0° C. to about 120° C. However, attemperatures below about 0° C. the polymerization rate slows and reactorresidence times .[.becomes.]. .Iadd.become .Iaddend.unreasonably long,while at temperatures above about 120° C. the polymerization rate is toohigh which results in excessive amounts of n-hexane-soluble products.Preferably, the temperature ranges from about 2° C. to about 95° C. andmost preferably from about 50° C. to about 80° C.

After polymerization catalyst residues contained in the polymericproduct can be deactivated by conventional methods such as washing withmethanol, water and caustic.

This invention is useful in polymerizing propylene to a normally solid,substantially crystalline polymer, although propylene also can bepolymerized with minor amounts up to about 30 wt. % of ethylene or othercopolymerizable alpha-olefins containing up to 10 carbon atoms to formrandom, pure-block, terminal block and multisegment copolymers.

The normally-solid propylene polymers prepared according to thisinvention have molecular weights ranging from about 50,000 to 5,000,000and typically range from about 200,000 to 2,000,000. The molecularweights of such propylene polymers can be controlled by methods known tothe art, such as by polymerizing in the presence of hydrogen in anamount determined by melt flow rate or by the molecular weightdistribution desired.

This invention is demonstrated but not limited by the followingExamples.

EXAMPLES I-VI

A series of propylene polymerizations were performed using various GroupVa or VII oxygen mineral acids as catalyst modifiers. In addition,control runs were performed without modifiers of this invention.

Modified catalyst was prepared in a nitrogen-purged dry box by adding ameasured amount of modifier dropwise with stirring to a portion ofdiethylaluminum chloride (25 wt. % in hexane). This mixture then wasadded dropwise with stirring to a suspension of titanium trichloride inhexane. The quantities were measured such that two moles of DEAC wereadded to one mole of TiCl₃.

Two milliliters of the resulting modified DEAC-TiCl₃ mixture werediluted with 200 milliliters of dry n-hexane in a 450 milliliterpressure bottle which was sealed and placed in a water bath maintainedat 160° F. Propylene was introduced into the bottle and a pressure of 40p.s.i.g. maintained for two hours while stirred magnetically. After twohours the bottle was cooled, uncapped and the contents filtered. A 10%aliquot was taken from the filtrate and evaporated. The remaining solidmaterial was weighed to determine the amount of Hexane Solubles. Thefiltered solid polypropylene was vacuum dried and weighed. Results areshown in Table I.

                  TABLE I                                                         ______________________________________                                                                            Hexane                                                               Yield    Solu-                                     Example Catalyst           (g/g of  bles                                      (Run)   (Molar Ratio)      TiCl.sub.3)                                                                            (Wt. %)                                   ______________________________________                                        (A)     DEAC/AA TiCl.sub.3.sup.(1)                                                                       133      3.41                                              (2/1)                                                                 I       DEAC/AA TiCl.sub.3 /Nitric                                                                       114      2.78                                              Acid (71%)                                                                    (2/1/0.04)                                                            II      DEAC/AA TiCl.sub.3 /Phosphoric                                                                   118.5    2.98                                              Acid (85%)                                                                    (2/1/0.04)                                                            III     DEAC/AA TiCl.sub.3 /Phos-                                                                        133.5    2.9                                               phorous Acid (30%)                                                            (2/1/0.04)                                                            IV      DEAC/AA TiCl.sub.3 /Nitric                                                                       96.5     2.53                                              Acid (71%)/HCl (37%)                                                          (2/1/0.04/0.02)                                                       (B)     DEAC/ABC-TiCl.sub.3.sup.(2)                                                                      425      1.62                                              (2/1)                                                                 V       DEAC/ABC-TiCl.sub.3 /Per-                                                                        388      0.74                                              chloric Acid (72%)                                                            (2/1/0.1)                                                             (C)     DEAC/ABC-TiCl.sub.3                                                                              335      1.02                                              (2/1)                                                                 VI      DEAC/ABC-TiCl.sub.3 /Nitric                                                                      261      0.8                                               Acid (71%)                                                                    (2/1/0.04)                                                            ______________________________________                                         .sup.(1) AA TiCl.sub.3  Stauffer Chemical Company Type 1.1                    .sup.(2) ABCTiCl.sub.3 (prepared according to U.S. Pat. No. 3,984,350)   

I claim:
 1. A catalyst composition for the polymerization of propyleneor mixtures of propylene and copolymerizable alpha-olefins, whichproduces low amounts of n-hexane-soluble polymer, comprising a titaniumtrihalide; an organoaluminum compound selected from the group consistingof dialkyl aluminum halide, trialkyl aluminum, a mixture thereof, and amixture of trialkyl aluminum with alkyl aluminum dihalide; and a.[.Group Va.]. .Iadd.nitrogen .Iaddend.or Group VII oxygen mineral acidin a molar ratio to titanium trihalide from about 0.005 to 1 to about0.7 to
 1. 2. The catalyst composition of claim 1 wherein the.[.transition metal compound.]. .Iadd.titanium trihalide .Iaddend.istitanium trichloride.
 3. The catalyst composition of claim 1 wherein themineral acid is an oxygen mineral acid of .[.nitrogen, phosphorus or.].chlorine.
 4. The catalyst composition of claim 1 wherein the mineralacid is nitric acid. .[.5. The catalyst composition of claim 1 whereinthe mineral acid is phosphoric acid..]. .[.6. The catalyst compositionof claim 1 wherein the mineral acid is phosphorous acid..].
 7. Thecatalyst composition of claim 1 wherein the mineral acid is perchloricacid.
 8. The catalyst composition of claim 3 wherein the titaniumtrihalide is titanium trichloride and the organoaluminum compound isdiethylaluminum chloride, triethylaluminum, a mixture thereof or amixture of triethylaluminum with ethylaluminum dichloride.
 9. Thecatalyst composition of claim 3 wherein the molar ratio of oxygenmineral acid to titanium tirhalide is about 0.02 to 1 to about 0.5 to 1.10. The catalyst composition of claim 4 wherein the molar ratio ofnitric acid to titanium trihalide is about 0.2 to 1 to about 0.5 to 1..[.11. The catalyst composition of claim 5 wherein the molar ratio ofphosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to1..]. .[.12. The catalyst composition of claim 6 wherein the molar ratioof phosphorous acid to titanium trihalide is about 0.02 to 1 to about0.5 to 1..].
 13. The catalyst composition of claim 7 wherein the molarratio of perchloric acid to titanium trihalide is about 0.02 to 1 toabout 0.1 to
 1. 14. The catalyst composition of claim 3 wherein thetitanium trihalide is titanium trichloride and the organoaluminumcompound is diethylaluminum chloride.
 15. A process for forming acatalyst composition for the polymerization of propylene or mixtures ofpropylene and copolymerizable alphaolefins, which produces low amountsof n-hexanesoluble polymer, comprising mixing in a suitable medium atitanium trihalide; an organoaluminum compound selected from the groupconsisting of dialkyl aluminum halide, trialkyl aluminum, mixturesthereof, and mixtures of trialkyl aluminum with alkyl aluminum dihalide;and a .[.Group Va.]. .Iadd.nitrogen .Iaddend.or Group VII oxygen mineralacid in a molar ratio to titanium trihalide from about 0.005 to 1 toabout 0.7 to
 1. 16. The process of claim 15 wherein the oxygen mineralacid is added to a solution of organoaluminum compound in an inerthydrocarbon then the resulting mixture is added to a mixture of titaniumtrihalide in an inert hydrocarbon.
 17. The process of claim 15 whereinthe titanium trihalide is titanium trichloride and the organoaluminumcompound is diethylaluminum chloride.
 18. The process of claim 16wherein the inert hydrocarbon is n-hexane.
 19. The process of claim 16wherein the mineral acid is nitric acid. .[.20. The process of claim 15wherein the mineral acid is phosphoric acid..]. .[.21. The process ofclaim 15 wherein the mineral acid is phosphorous acid..].
 22. Theprocess of claim 15 wherein the mineral acid is perchloric acid. .Iadd.23. A catalyst composition for the polymerization of propylene ormixtures of propylene and copolymerizable alpha-olefins, which produceslow amounts of n-hexane-soluble polymer, comprising a titaniumtrihalide; a dialkyl aluminum halide; and a phosphorous oxygen mineralacid in a molar ratio to titanium trihalide from about 0.005 to 1 toabout 0.5 to
 1. .Iaddend..Iadd.
 24. The catalyst composition of claim 23wherein the mineral acid is phosphoric acid. .Iaddend..Iadd.
 25. Thecatalyst composition of claim 23 wherein the mineral acid is phosphorousacid. .Iaddend..Iadd.
 26. The catalyst composition of claim 23 whereinthe titanium trihalide is titanium trichloride. .Iaddend..Iadd.
 27. Thecatalyst composition of claim 24 wherein the molar ratio of phosphoricacid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1..Iaddend..Iadd.
 28. The catalyst composition of claim 25 wherein themolar ratio of phosphorous acid to titanium trihalide is about 0.02 to 1to about 0.5 to
 1. .Iaddend. .Iadd.
 29. A process for forming a catalystcomposition for the polymerization of propylene or mixtures of propyleneand copolymerizable alpha-olefins, which produces low amounts ofn-hexane-soluble polymer, comprising mixing in a suitable medium, atitanium trihalide; a dialkyl aluminum halide; and a phosphorus oxygenmineral acid in a molar ratio to titanium trihalide from about 0.005 to1 to about 0.5 to
 1. .Iaddend..Iadd.
 30. The process of claim 29 whereinthe oxygen mineral acid is added to a solution of dialkyl aluminumhalide in an inert hydrocarbon, then the resulting mixture is added to amixture of titanium trihalide in an inert hydrocarbon. .Iaddend..Iadd.31. The process of claim 30 wherein the inert hydrocarbon is n-hexane..Iaddend..Iadd.
 32. The process of claim 29 wherein the mineral acid isphosphoric acid. .Iaddend..Iadd.
 33. The process of claim 29 wherein themineral acid is phosphorous acid. .Iaddend.